Precursor polymer preparation

Nevertheless, conductive polymers have also been synthesized using other techniques, such as chain polymerization, step-growth polymerization, chanical vapor deposition, solid-state polymerization, soluble-precursor polymer preparation, and concentrated anulsion polymerization, to name just a few. Most of these techniques, however, are time consuming and involve the use of costly chemicals. 

Experiments have shown that polymers are inexpensive to manufacture and can be prepared as films, which is very important for device application. Conductive polymers may be synthesized by any one of the following techniques (Kumar and Sharma 1998) (1) chemical polymerization, (2) electrochemical polymerization, (3) photochemical polymerization, (4) metathesis polymerization, (5) concentrated emulsion polymerization, (6) inclusion polymerization, (7) solid-state polymerization, (8) plasma polymerization, (9) pyrolysis, and (10) soluble precursor polymer preparation. Several methods of... 

The polydispersity index for precursor polymers prepared via the Durham route was only in the range of 1.8-2.8 [88]. Krouse and Schrock were able to improve on the metathesis ROMP method and prepared a series of acetylene block copolymers with success both in controlling the molecular weight and in achieving low polydispersity [82]. Compared to a living polymerization process, the well-controlled ROMP precursor polymers can be grown continuously... 

For small-scale preparation of samples for scientific studies, the precursor polymer may be dissolved in xylene at 80°C, followed by addition of the cation source. A gelled fluid is normally obtained immediately, and the ionomer is recovered as a powder by chopping the gel in a large excess of acetone using a laboratory blender. 

Even with improvement in properties of polyacetylenes prepared from acetylene, the materials remained intractable. To avoid this problem, soluble precursor polymer methods for the production of polyacetylene have been developed. The most highly studied system utilizing this method, the Durham technique, is shown in equation 2. 

Poly(arylene vinylenes). The use of the soluble precursor route has been successful in the case of poly(arylene vinylenes), both those containing ben2enoid and heteroaromatic species as the aryl groups. The simplest member of this family is poly(p-phenylene vinylene) [26009-24-5] (PPV). High molecular weight PPV is prepared via a soluble precursor route (99—105). The method involves the synthesis of the bis-sulfonium salt from /)-dichloromethylbenzene, followed by a sodium hydroxide elimination polymerization reaction at 0°C to produce an aqueous solution of a polyelectrolyte precursor polymer (11). This polyelectrolyte is then processed into films, foams, and fibers, and converted to PPV thermally (eq. 8). 

Heteroaromatic ring stmctures can also be incorporated into poly(arylene vinylene) stmctures using the same precursor polymer method shown for PPV. Poly(thienylene vinylene) (13) (113—118) and poly(furylene vinylene) (14) (119,120) have been prepared in this manner. In addition, alkoxy-substituted poly(thienylene vinylenes) (15) (119,121) have been synthesized. Various copolymers containing phenjiene, thienylene, and furylene moieties have also been studied (120,122,123). 

In both of the above cases, the PPV films were prepared from precursor polymers and converted at elevated temperatures with a minute amount of oxygen... 

Other poly(2,5-dialkoxy-1,4-phenylene vinylene)s have been prepared in a similar fashion [34, 35, 40, 41]. Alternatively, a soluble a-halo precursor polymer 17 may be obtained by using less than one equivalent of base (Scheme 1-6). This may then be converted into fully conjugated material 16 by thermal treatment. This halo-precursor route may be preferred if the fully conjugated material has limited solubility or if incomplete conversion is desired. 

In a classical multi-step route the critical point is to conduct (he ring closure quantitatively and regioseleclively. In the synthesis of I.PPP, the precursor polymer 13 is initially prepared in an aryl-aryl coupling from an aromatic diboronic acid and an aromatic dibromoketone. 

Mohanty et al. were the first to introduce pendent r-butyl groups in die polymer backbones. The resulting material was quite soluble in aprotic dipolar solvents.83 The PEEK precursors were prepared under a mild reaction condition at 170°C. The polymer precursor can be converted to PEEK in die presence of Lewis acid catalyst A1C13 via a retro Friedel-Crafts alkylation. Approximately 50% of die rerr-butyl substitutes were removed due to die insolubility of the product in die solvent used. Later, Risse et al. showed diat complete cleavage of f< rf-butyl substitutes could be achieved using a strong Lewis acid CF3SO3H as both die catalyst and the reaction medium (Scheme 6.15).84... 

This idea was realized impressively in 1991 with the first synthesis of a soluble, conjugated ladder polymer of the PPP-type [41]. This PPP ladder polymer, LPPP 26, was prepared according to a so-called classical route, in which an open-chain, single-stranded precursor polymer was closed to give a double-stranded ladder polymer. The synthetic potential of the so-called classical multi-step sequence has been in doubt for a long time in the 1980s synchronous routes were strongly favoured as preparative method for ladder polymers. 

Mohammad Jafar Soltanian Fard-Jahromi and Ali Morsali (2010) Sonochemical synthesis of nanoscale mixed-ligands lead(II) coordination polymers as precursors for preparation of Pb2(S04)0 and PbO nanoparticles thermal, structural and X-ray powder diffraction studies. Ultrason Sonochem 17(2) 435-440... 

In the via precursor method, however, it is difficult to prepare the ji-conjugated polymers with ideally developed -conjugation system the -conjugated polymer chains contain many conformational defects because the jc-conjugated chains are caused to develop from disordered precursor polymer, which form random coil conformation, in solid state. For the preparation of polymers with well-developed jc-conjugation system by the via precursor method, accordingly, it is necessary to introduce orientational and conformational orderliness of the precursor polymers in the films. 

Three kinds of PAV films was prepared using methoxy pendant precursors. The chemical structures and synthetic route of the PAV films used in this study are shown in Fig. 19. The details of synthesis of the methoxy pendant precursors have been described in refs. 29 and 30. The precursors were soluble in conventional organic solvents, for example, chloroform, dichloromethane, benzene and so on. The precursor polymer thin films were spin-coated on fused quartz substrates from the chloroform solutions. The precursor films were converted to PAV films by the heat-treatment at 250 0 under a nitrogen flow with a slight amount of HC1 as a catalyst. This method provided high performance PAV films with excellent optical quality. 

Figure 21 shows three possible routes to obtain oriented PAV films by the LB technique. In these route, it is anticipated that orientational orderliness of precursor polymers is introduced in the precursor LB films through the formation of two-dimensionally oriented monolayer of a polyelectrolyte precursor-anionic amphiphile polyion complex at the air/subphase interface and orientation of the precursor monolayers along the dipping direction dining the deposition process. As a result, it is expected to obtain oriented PAV LB films with well-developed jt-coryugation system. In this study, we successfully prepared oriented PAV films using two routes of them, b-1 and b-2 route [35-37]. The chemical structures of PAVs, their polyelectrolyte precursors and an anionic amphiphile used in this study are shown in Fig.22. 

Using the b-1 route, PPV LB films were successfully fabricated [35], The precursor polymer of PPV was prepared according to ref.27. Anionic amphiphile 2C12SUC was purchased from Sogo Pharmaceutical Co. and used without further purification. An aqueous solution of the precursor polymer was added dropwise to an aqueous 2C12SUC solution. Then, the precursor-anionic amphiphile polyion complex was precipitated. The precipitates were filtered and washed with deionized... 

In the preparation of the MOPPV LB films, the polyion complex monolayer were formed by the adsorption of the precursor onto the anionic amphiphile monolayer (route b-2 in Fig.5) [36,37]. The monolayer of 2C12SUC was spread on a aqueous solution of the MOPPV precursor polymer (repeating unit concentration about 10"4 M). The monolayer was allowed to stand for 4 hours to adsorb the precursor after being compressed to a surface pressure of 30 mNm 1. The monolayer was deposited on fused quartz substrate by the LB technique. At last, the deposited polyion complex was converted to MOPPV by the heat treatment at 200 C in vacuo (about 10 2 torr). 

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